Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D22/00—Producing hollow articles
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
  • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D23/00—Producing tubular articles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
  • B32B1/08—Tubular products
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
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  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
  • B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
  • B65D85/30—Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure
  • B65D85/34—Containers, packaging elements or packages, specially adapted for particular articles or materials for articles particularly sensitive to damage by shock or pressure for fruit, e.g. apples, oranges or tomatoes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C2949/00—Indexing scheme relating to blow-moulding
  • B29C2949/07—Preforms or parisons characterised by their configuration
  • B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/0005—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fibre reinforcements
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
  • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
  • B29C49/04—Extrusion blow-moulding
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
  • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
  • B29C49/06—Injection blow-moulding
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
  • B29C49/08—Biaxial stretching during blow-moulding
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2311/00—Use of natural products or their composites, not provided for in groups B29K2201/00 - B29K2309/00, as reinforcement
  • B29K2311/10—Natural fibres, e.g. wool or cotton
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0037—Other properties
  • B29K2995/0059—Degradable
  • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/08—Reinforcements
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
  • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2307/00—Properties of the layers or laminate
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  • B32B2307/716—Degradable
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B32B2439/00—Containers; Receptacles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L97/00—Compositions of lignin-containing materials
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• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
  • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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  • Y10T428/00—Stock material or miscellaneous articles
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• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/30—Woven fabric [i.e., woven strand or strip material]

Definitions

• polylactide-based composite materials that can include a polylactide-based polymer matrix, reinforcement fibers derived from a renewable resource such as flax, kenaf or cotton, and a protective inhibitory agent.
• An inhibitory agent can at least partially block or prevent the passage of a factor across a structure formed including the composite material and can, in one embodiment, improve the capability of the composite material in limiting or preventing the passage of a potentially damaging factor into the interior of a formed structure.
• the composite material can at least partially prevent or restrict factors such as oxygen, ultraviolet (UV) radiation, microbial agents, fungal agents, and the like from passage across the wall of the structure.
• a polymeric composite material can include a fibrous material in an amount of less than about 5% by weight of the composite material.
• a polymeric composite material can include an inhibitory agent in an amount of between about 1 and about 100 ⁇ g/mL container volume for each month of storage life of a substance to be held in the container.
• a polylactide-based polymer that can be used in a composite material as described herein can be, for instance, a polylactide-based homopolymer or copolymer or a polymer blend such as a polylactide/polyhydroxy alkanoate polymer blend.
• Inhibitory agents can be derived from natural resources.
• One exemplary inhibitory agent can be a natural anti-oxidant such as turmeric.
• an inhibitory agent can be released over time from the composite, for instance as the composite material degrades.
• Structures that can be formed from a composite polymeric material can include containers, such as, for example, molded containers.
• a molded container can be, for example, an injection molded or an injection blow molded container.
• a container as described herein can be completely biodegradable.
• a packaging material for an agricultural product can include a polylactide-based polymer and reinforcement fibers formed of the same agricultural product as can be packaged with the material.
• a packaging material can be a fabric that can include yarns formed of a polylactide-based composite material.
• the packaging material can be designed for use with cotton.
• the packaging material can also include an inhibitory agent as described above for additional protection of the contents to be held within the packaging material.
• Methods for forming a polylactide-based composite material can include, for instance, providing a polylactide- based polymer resin having a moisture content of less than about 50 ppm, combining the resin with reinforcement fibers in an amount of less than about 5% by weight of the polymer, combining the polymer with an inhibitory agent, and then molding the mixture to obtain the final product.
• Figure 1 illustrates an exemplary molded product formed from a composite material as disclosed herein;
• FIG. 2 illustrates a thermal gravimetric analysis (TGA) of exemplary natural fibers that can be used in forming disclosed composites as well as TGA of several exemplary polymeric composite materials;
• Figure 3 illustrate several exemplary containers formed as described in the Example section
• Figure 4 graphically illustrates energy transmission characteristics of containers formed as described in the Example section.
• Figure 5 graphically illustrates oxygen ingress over time for containers formed as described in the Example section.
• the present disclosure includes methods and materials that can be used to form environmentally-friendly polymeric materials as well as products that can be formed from such materials.
• disclosed polymeric composite materials can include a polymeric matrix in combination with a plurality of natural fibers.
• all of the components of a composite material can be derived from renewable resources.
• Disclosed composite polymeric materials can be formed into any of a large variety of products via low temperature processing techniques. In such embodiments, both the materials and the methods used to form products from the materials can be environmentally friendly.
• a composite polymeric material can include a lactide-based polymeric matrix in combination with a plurality of fibers, both of which can be derived from renewable resources.
• the term 'lactide-based polymer' is intended to by synonymous with the terms polylactide, polylactic acid (PLA) and polylactide polymer, and is intended to include any polymer formed via the ring opening polymerization of lactide monomers, either alone (i.e., homopolymer) or in mixture or copolymer with other monomers.
• the term is also intended to encompass any different configuration and arrangement of the constituent monomers (such as syndiotactic, isotactic, and the like).
• the polymeric composites disclosed herein can include any of a variety of environmentally friendly beneficial agents such as, for instance, anti- oxidation agents, anti-microbial agents, anti-fungal agents, and the like that can provide desired characteristics to products.
• beneficial agents can also be derived from renewable resources.
• a polymeric composite can include one or more inhibitory agents that can provide a formed polymeric structure with an improved capability in preventing or limiting the passage of damaging factors into, through, or across the finished products.
• all of the components of a polymeric composite material e.g., the polymers, the fibers, and any added agent(s) can be combined and processed to form blended lactide polymer resin in the form of beads or pellets. Accordingly, the pre-formed resin pellets can be ready for processing in a product fabrication process. As such, a product formation process can not only be a low cost, low energy formation process, but can also be quite simple.
• a lactide-based polymeric matrix can be derived from lactic acid. Lactic acid is produced commercially by fermentation of agricultural products such as whey, cornstarch, potatoes, molasses, and the like.
• a lactide monomer can first be formed by the depolymerization of a lactic acid oligomer.
• production of lactide was a slow, expensive process, but recent advances in the art have enabled the production of high purity lactide at reasonable costs. As such processes are generally known to those of skill in the art; they are not discussed at length herein.
• One embodiment of a formation process can include formation of a lactide-based polymer through the ring-opening polymerization of a lactide monomer.
• commercially available polymers such as those exemplified below, can be used.
• the lactide-based polymeric matrix of a composite material can include a homopolymer formed exclusively from polymerization of lactide monomers.
• lactide monomer can be polymerized in the presence of a suitable polymerization catalyst, generally at elevated heat and pressure conditions, as is generally known in the art.
• the catalyst can be any compound or composition that is known to catalyze the polymerization of lactide.
• Such catalysts are well known, and include alkyl lithium salts and the like, stannous octoate, aluminum isopropoxide, and certain rare earth metal compounds as described in U.S. Patent No. 5,028,667 and which is incorporated herein by reference.
• the particular amount of catalyst used can vary generally depending on the catalytic activity of the material, as well as the temperature of the process and the polymerization rate desired. Typical catalyst concentrations include molar ratios of lactide to catalyst of between about 10:1 and about 100,000:1, and in one embodiment from about 2,000:1 to about 10,000:1.
• a catalyst can be distributed in a starting lactide monomer material. If a solid, the catalyst can have a relatively small particle size.
• a catalyst can be added to a monomer solution as a dilute solution in an inert solvent, thereby facilitating handling of the catalyst and its even mixing throughout the monomer solution.
• the process can also include steps to remove catalyst from the mixture following the polymerization reaction, for instance one or more leaching steps.
• a polymerization process can be carried out at elevated temperature, for example, between about 95 0 C and about 200°C, or in one embodiment between about 110 0 C and about 170 0 C, and in another embodiment between about 140 0 C and about 16O 0 C.
• the temperature can generally be selected so as to obtain a reasonable polymerization rate for the particular catalyst used while keeping the temperature low enough to avoid polymer decomposition.
• polymerization can take place at elevated pressure, as is generally known in the art. The process typically takes between about 1 and about 72 hours, for example between about 1 and about 4 hours.
• Polylactide homopolymer obtainable from commercial sources can also be utilized in forming the disclosed polymeric composite materials.
• poly(L-lactic acid) available from Polysciences, Inc, Natureworks, LLC, Cargill, Inc., Mitsui (Japan), Shimadzu (Japan), or Chronopol can be utilized in the disclosed methods.
• a lactide-based polymer matrix can include polymers formed from lactide monomer or oligomer in combination with one or more other polymeric materials.
• lactide can be co-polymerized with one or more other monomers or oligomers derived from renewable resources to form a lactide-based copolymer that can be incorporated in a polymeric composite material.
• the secondary monomers of the copolymer can be materials that are at least recyclable and, in one embodiment, completely and safely biodegradable so as to present no hazardous waste issues upon degradation of the copolymer.
• a lactide monomer can be co-polymerized with a monomer or oligomer that is anaerobically recyclable, which can improve the recyclability of the copolymer as compared to that of a PLA homopolymer.
• Polylactide copolymers for use in the disclosed composite materials can be random copolymers or block copolymers, as desired.
• a polymeric composition can include a polymer blend.
• a lactide-based polymer or copolymer can be blended with another polymer, for example a recyclable polymer such as polypropylene, polyethylene terephthalate, polystyrene, polyvinylchloride or the like.
• a polymer blend can be utilized including a secondary polymer that can also be formed of renewable resources, as can be PLA.
• a polymer blend can include a PLA polymer or copolymer in combination with a polyhydroxy alkanoate (PHA).
• PHAs are a member of a relatively new class of biomaterials prepared from renewable agricultural resources through bacterial fermentation. A variety of PHA compositions are available under the trade name NODAXTM from the Proctor & Gamble corporation of Cincinnati, Ohio.
• a polymeric blend can include a PLA homopolymer or co-polymer as at least about 50% by weight of the polymer blend.
• a polymeric blend can include at least about 70% PLA by weight of the blend, or higher in other embodiments, for instance greater than about 80% PLA by weight of the blend.
• disclosed composite materials can also include a plurality of natural fibers that can be derived from renewable resources and can be biodegradable. Fibers of the composite materials can, in one embodiment, reinforce mechanical characteristics of the composite materials. For instance fibers can improve the strength characteristics of the materials. The natural fibers can offer other/additional benefits to the disclosed composites, such as improved compatibility with secondary materials, improved biodegradability of the composite materials, attainment of particular aesthetic characteristics, and the like. [0033] Natural fibers suitable for use in the presently disclosed composites can include plant, mineral, and animal-derived fibers. Plant derived fibers can include seed fibers and multi-cellular fibers which can further be classified as bast, leaf, and fruit fibers.
• Plant fibers that can be included in the disclosed composites can include cellulose materials derived from agricultural products including both wood and non-wood products.
• fibrous materials suitable for use in the disclosed composites can include plant fibers derived from families including, but not limited to dicots such as members of the Linaceae (e.g., flax), Urticaceae, Tiliaceae (e.g., jute), Fabaceae, Cannabaceae, Apocynaceae, and Phytolaccaceae families, and, in some embodiments, monocots such as those of the Agavaceae family.
• the fibers can be derived from plants of the Malvaceae family, and in one particular embodiment, those of the genera Hibisceae (e.g., kenaf, beach hibiscus, rosselle) and/or those of the genera Gossypieae (e.g., cottons and allies).
• Hibisceae e.g., kenaf, beach hibiscus, rosselle
• Gossypieae e.g., cottons and allies.
• cotton fibers can be utilized in the disclosed composites.
• cotton fibers can first be separated from the seed and subjected to several mechanical processing steps as are generally known to those of skill in the art to obtain a fibrous material for inclusion in a composite.
• flax fibers can be incorporated into the disclosed composites.
• Processed flax fibers can generally range in length from 0.5 to 36 in with a diameter from 12-16 micrometers.
• Linseed which is flax grown specifically for oil, has a well established market and millions of acres of flaxseed are grown annually for this application, with the agricultural fiber residue unused.
• agricultural production of flax has the potential to provide dual cropping, jobs at fiber processing facilities, and a value added crop in rotation.
• Reinforcement fibers of a composite material can include bast and/or stem fibers extracted from plants according to methods generally known in the art.
• the inner pulp of a plant can be a useful byproduct of the disclosed methods, as the pulp can beneficially be utilized in many known secondary applications, for instance in paper-making processes.
• the fibrous reinforcement materials can include bast fibers of up to about 10 mm in length.
• kenaf bast fibers between about 2 mm and about 6 mm in length can be utilized as reinforcement fibers.
• a composite polymeric material can generally include a fibrous component in an amount of up to about 50% by weight of the composite.
• a composite material can include a fibrous component in an amount between about 10% and about 40% by weight of the composite.
• a composite material can include a fibrous component in an amount of about 30% by weight of the composite.
• the fiber component of the composite materials can serve merely to provide reinforcement to the polymeric matrix and improve strength characteristics of the material.
• the fibrous component can optionally or additionally provide particular aesthetic qualities to the composite material and/or products formed therefrom.
• particular fibers or combinations of fibers can be included in a composite material to affect the opacity, color, texture, and overall appearance of the material and/or products formed therefrom.
• cotton, kenaf, flax, as well as other natural fibers can be included in the disclosed composites either alone or in combination with one another to provide a composite material having a unique appearance and/or texture for any of a variety of applications.
• a polymeric composite material can include one or more inhibitory agents that can provide desirable characteristics to the material and/or products formed therefrom.
• a composite can include one or more natural and/or biodegradable agents that can be derived from renewable resources such as anti-oxidants, antimicrobial agents, anti-fungal agents, ultra-violet blockers, ultra-violet absorbers, and the like that can be completely and safely biodegradable.
• one or more inhibitory agents can improve protection of materials on one side of the formed polymeric material from one or more potentially damaging factors.
• one or more inhibitory agents can provide increased prevention of the passage of potentially harmful factors (e.g., oxygen, microbes, UV light, etc.) across a structure formed of the composite material and thus offer improved protection of materials held on one side of the composite polymeric material from damage or degradation.
• a composite polymeric material can be designed to release an inhibitory agent from the matrix as the composite degrades, at which time the inhibitory agent can provide the desired activity, e.g., anti-microbial activity, at a surface of the polymeric composite.
• Exemplary inhibitory agents can include without limitation, one or more natural anti-oxidants such as turmeric, burdock, green tea, garlic, bilberry, elderberry, ginkgo biloba, grape seed, milk thistle, lutein (an extract of egg yolks, com, broccoli, cabbage, lettuce, and other fruits and vegetables), olive leaf, rosemary, hawthorn berries, chickweed, capsicum (cayenne), and blueberry pulp.
• natural anti-oxidants such as turmeric, burdock, green tea, garlic, bilberry, elderberry, ginkgo biloba, grape seed, milk thistle, lutein (an extract of egg yolks, com, broccoli, cabbage, lettuce, and other fruits and vegetables), olive leaf, rosemary, hawthorn berries, chickweed, capsicum (cayenne), and blueberry pulp.
• One or more natural anti-microbial agents can be included in a polymeric composite.
• exemplary natural anti-microbial agents can include berberine, an herbal anti-microbial agent that can be extracted from plants such as goldenseal, coptis, barberry, Oregon grape, and yerba mensa.
• Other natural anti-microbial agents can include, but are not limited to, extracts of propolis, St. John's wort, cranberry, garlic, E. cochinchinensis and S. officinalis, as well as anti-microbial essential oils, such as those that can be obtained from cinnamon, clove, or allspice, and anti-microbial gum resins, such as those obtained from myrrh and guggul.
• exemplary inhibitory agents that can be included in the composite materials can include natural anti-fungal agents such as, for example, tea tree oil and resveratrol (a phytoestrogen found in grapes and other crops), or naturally occurring ultraviolet light blocking compounds such as mycosporine-like amino acids found in coral.
• natural anti-fungal agents such as, for example, tea tree oil and resveratrol (a phytoestrogen found in grapes and other crops)
• naturally occurring ultraviolet light blocking compounds such as mycosporine-like amino acids found in coral.
• the composite polymeric materials can include multiple inhibitory agents, each of which can bring one or more desired protective capacities to the composite.
• an inhibitory agent such as those described above can be included in an amount of less than about 10% by weight of the composite material. In other embodiments, an agent can be included at higher weight percentage. In one embodiment, the preferred addition amount can depend on one or more of the activity level of the agents upon potentially damaging factors, the amount of material to be protected by a structure formed including the composite material, the expected storage life of the material to be protected, and the like. For example, in one embodiment, an inhibitory agent can be incorporated into a composite polymeric material in an amount of between about 1 ⁇ g/ml_ material to be protected/month of storage life to about 100 ⁇ g/ml_ material to be protected/month of storage life.
• a composite polymeric material can optionally include one or more additional additives as are generally known in the art. For example, a small amount (e.g., less than about 5% by weight of the composite material) of any or all of plasticizers, stabilizers, fiber sizing, polymerization catalysts, or the like can be included in the composite formulations.
• any additional additives to the composite materials can be at least recyclable and non-toxic, and, in one embodiment, can be formed from renewable resources.
• the various components of a polymeric composite material can be suitably combined prior to forming a polymeric structure.
• the components can be melt or solution mixed in the formulation desired in a formed structure and then formed into pellets, beads, or the like suitable for delivery to a formation process.
• a product formation process can be quite simple, with little or no measuring or mixing of components necessary prior to the formation process (e.g., at the hopper).
• a chaotic mixing method such as that described in U.S. Patent 6,770,340, to Zumbrunnen, et al., which is incorporated herein by reference, can be used to combine the components of the polymeric composite.
• a chaotic mixing process can be used, for example, to provide the composite material with a particular and selective morphology with regard to the different phases to be combined in the mixing process, and in particular, with regard to the polymers, the fibrous reinforcement materials, and the inhibitory agents to be combined in the mixing process.
• a chaotic mixing process can be utilized to form a composite material including one or more inhibitory agents concentrated at a predetermined location in the composite, so as to provide for a controlled release of the agents, for instance a timed-release of the agents from the composite as the polymeric component of the composite material degrades over time.
• the composite polymeric material can be formed into a desired structure via a low energy formation process.
• One exemplary formation process can include providing the components of the composite materials to a product mold and forming the product via an in situ polymerization process.
• reinforcement fibers, one or more inhibitory agents, and the desired monomers or oligomers can be solution mixed or melt mixed in the presence of a catalyst, and the polymeric product can be formed in a single step in situ polymerization process.
• an in situ polymerization formation process can be carried out at ambient or only slightly elevated temperatures, for instance, less than about 75 0 C. Accordingly, the activity of the inhibitory agents can be maintained through the formation process, with little or no loss in activity.
• In situ polymerization can be preferred in some embodiments due to the more favorable processing viscosity and degree of mixing that can be attained.
• a monomer solution can describe a lower viscosity than a solution of the polymerized material.
• a reactive injection molding process can be utilized with a low viscosity monomer solution though the viscosity of the polymer is too high to be processed similarly.
• better interfacial mixing can occur by polymerization in situ in certain embodiments, and better interfacial mixing can in turn lead to better and more consistent mechanical performance of the final molded structure.
• a formation process can include forming a polymeric structure from a polymeric melt, for instance in an extrusion molding process, an injection molding process or a blow molding process.
• injection molding processes include any molding process in which a polymeric melt or a monomeric or oligomeric solution is forced under pressure, for instance with a ram injector or a reciprocating screw, into a mold where it is shaped and cured.
• Blow molding processes can include any method in which a polymer can be shaped with the use of a fluid and then cured to form a product.
• Blow molding processes can include extrusion blow molding, injection blow molding, and stretch blow molding, as desired.
• Extrusion molding methods include those in which a melt is extruded from a die under pressure and cured to form the final product, e.g., a film or a fiber.
• polymeric structures can be formed utilizing less energy than previously known melt processes.
• melts can be processed at temperatures about 100 0 F lower than molding temperatures necessary for polymers such as polypropylene, polyvinlyl chloride, polyethylene, and the like.
• composite polymeric melts as disclosed herein can be molded at temperatures between about 170°C to about 180°C, about 100°C less than many fiberglass/polypropylene composites.
• a composite polymeric material as disclosed herein can be formed as a container, and in one particular embodiment, a container suitable for holding and protecting environmentally sensitive materials such as biologically active materials including pharmaceuticals and nutraceuticals.
• the term 'pharmaceutical' is herein defined to encompass materials regulated by the United States government including, for example, drugs and other biologies.
• the term 'nutraceutical' is herein defined to refer to biologically active agents that are not necessarily regulated by the United States government including, for example, vitamins, dietary supplements, and the like.
• a polymeric composite material can include one or more inhibitory agents that can prevent passage of one or more factors across a formed structure. Accordingly, the polymeric composite material can help to prevent the degradation of the contents of a container from damage due to for instance, oxidation, ultraviolet energy, and the like.
• formed structures can include a natural anti-oxidant in the composite polymeric material and can be utilized to store and protect oxygen-sensitive materials, such as oxygen-sensitive pharmaceuticals or nutraceuticals, from oxygen degradation.
• Formed structures incorporating the composite materials can include laminates including the disclosed composite materials as one or more layers of the laminate.
• a laminate structure can include one or more layers formed of composite materials as herein described so as to provide particular inhibitory agents at predetermined locations in the laminate structure.
• Such an embodiment can, for instance, provide for a controlled release of the inhibitory agents, for instance a timed-release of an agent from the composite as the adjacent layers and the polymeric component of the composite material degrade over time.
• a laminate can include an impermeable polymeric layer on a surface of the structure, e.g., on the interior surface of a container (e.g., bottle or jar) or package (e.g., blister pac for pills).
• an extruded film formed from a composite polymeric material can form one or more layers of such a laminate structure.
• an impermeable PLA-based film can form an interior layer of a container so as to, for instance, prevent leakage, degradation or evaporation of liquids that can be stored in the container.
• Such an embodiment may be particularly useful when considering the storage of alcohol-based liquids, for instance, nutraceuticals in the form of alcohol-based extracts or tinctures.
• a composite polymeric material can form a structure to contain and protect environmentally sensitive materials such as environmentally sensitive agricultural materials including processed or unprocessed crops.
• environmentally sensitive materials such as environmentally sensitive agricultural materials including processed or unprocessed crops.
• a composite polymeric material can be melt processed to form a fiber or a yam and the fibers or yams can be further processed to form a fabric, for instance a woven, nonwoven, or knitted fabric, that can be utilized to protect and/or contain an environmentally sensitive material such as a recently harvested agricultural material or optionally a secondary product formed from the agricultural material.
• containers can be specifically designed for the agricultural material that they will protect and contain.
• containers can be particularly designed to contain a specific agricultural material, and the fibrous component of the composite used to form the container can be derived from that same agricultural material.
• a composite polymeric material can include a degradable polymeric matrix and a plurality of cotton fibers. This composite material can then be melt processed to form a structure, e.g., a bag, a wrap, or the like specifically designed to contain and/or protect cotton.
• a composite polymeric material can include a degradable, PLA-based polymeric component and a fibrous flax component, and the composite can form a container specifically designed for the containment/protection of either unprocessed or processed flax.
• the contents e.g., the cotton, flax, etc.
• the contents can still be suitable and safe for further processing, in particular as the 'contaminants' that have inadvertently come into contact with the contents are naturally derived materials, and in the case of the fibrous components, derived from the same crop as the contents of the container.
• a 100 mL single neck flask was dried under flame and connected to an overhead stir.
• various amounts of commercial L-polylactide polymer obtained from Cargill Dow Polymers, LLC, MW ca. 190,000 Mn
• THF Tetrahydrofuran
• various amounts of Kenaf fiber (2-5 mm) were added to the solution in separate runs, as indicated below in Table 1.
• a control sample including no fiber addition was formed.
• the PLA/kenaf mixture was stirred for 2 hr.
• the resulting solution was added to a Teflon mold and dried on the bench top overnight followed by drying under vacuum at 40 0 C for 1 hr.
• Table 4 lists the different material blends that were prepared and molded according to the process. All materials were prepared with virgin PLA, product number 7032D, obtained from NatureWorks® LLC. All addition amounts are given as a weight percent unless otherwise noted.
• kenaf was chopped several times to obtain fibers approximately % inch in length. The material was then filtered through a mesh screen. The material remaining following filtering was chopped and filtered again until suitable amount of fiber was obtained. The kenaf fibers and virgin PLA (and turmeric for blend no. 3) were mixed through simultaneous addition to a Mylar bag followed by manual shaking. As with the cotton blends, the material was manually fed into the twin-screw.
• the resin was dried at 100 0 C overnight to reduce the moisture level below 50ppm. Feed materials were ground into small particle sizes before extrusion.
• bottles were analyzed for UV transmission between 300 and 400nm using a Perkin-Elmer Lambda 9 UV/Vis/NIR Spectrophotometer. Beer-Lambert's law was used to correct the data to a 0.012" thickness that is the common wall thickness for PET bottles.
• Three sets of PLA containers were evaluated for UV transmission: blend no. 2, blend no. 3 and blend no. 6. Results are illustrated in Table 8 and in Figure 4. As can be seen, the UV transmission for blend no. 2, including both cotton fibers and turmeric, had the lowest transmission rate of the three sets tested. Bottles formed from blend no. 3, including both kenaf fibers and turmeric, exhibited lower UV transmission than those formed of blend no.
• Bottles were also tested for water vapor transmission using ASTM method F1249. For this method, one empty bottle was tested using Mocon equipment at 100 0 F and 100% relative humidity and the results were corrected to sea level pressure. The results are shown in Table 10 below. Table 10
• Bottles were tested for O 2 permeation rate.
• the bottles were placed onto a Mocon station with epoxy in a 42-48% relative humidity atmosphere on the inside of the container.
• the outside of the container was exposed to a 72°F, 50% relative humidity environment.
• the equilibrated oxygen permeation is shown in the table below for each blend tested.
• the permeation rate for a PET container would be in the 0.040-0.050 cc/pkg/day range for this type of container.
• Oxygen permeation was also evaluated using the Mocon headspace technique.
• five bottles of each sample number type were prepared for long term oxygen permeation testing by applying a metal washer fixed with a rubber septum onto the container finish. Approximately 5OmL of tap water was added to each container and then the bottles were affixed to a purging system. These bottles were then flushed with 99.999% nitrogen to reduce the internal oxygen concentration below 200ppm.
• the initial oxygen concentration was determined by pulling a small sample from each container and analyzing it on a Mocon PAC CHECK 450 Oxygen Analyzer. The bottles were then stored in a controlled environment at 72°F and 45-50% relative humidity. The bottles were removed from the chamber and sampled periodically with the Mocon PAC Check 450 to determine the oxygen ingress over time. The averaged results collected to date are shown in Table 12, below and Figure 5. Table 12

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